Perfume compositions

ABSTRACT

A novel ester comprising the reaction product of longifolene and formic acid, perfume and fragrance compositions containing same and process for producing such reaction product.

United. States Patent Wight et al. 1451 0a. 1, 1974 PERFUME COMPOSITIONS [56] References Cited [75] Inventors: Christian F. Wight, Rio de Janeiro, UNITED STATES PATENTS Braid; Rumson, 3,745,131 7/1973 Curtis et al. 252/522 [731 Assignee= zf fi t z f g g rk N Y FOREIGN PATENTS OR APPLICATIONS g e o 1,225,158 3/1971 Great Britain 260/488 [22] Filed: Jan. 6, 1972 [2]]. Appl 215,910 Primary ExaminerSam Rosen Related US. Application Data [62] Division of Ser. No. 37,333, May 14, 1970, [57] ABSTRACT abandoned. A novel ester comprising the reaction product of Iongifolene and formic acid, perfume and fragrance com- [52] US. Cl. 252/522 positions containing same and process for producing [51] Int. Cl Cllb 9/00 such reaction product. [58] Field of Search 252/522; 260/488 B 2 Claims, No Drawings PERFUME COMPOSITIONS This application is a division of US. application Ser. No. 37,333 filed May 14, 1970, now abandoned.

The present invention relates in general to perfumery and in particular to the provision of a novel substance beneficially adapted for use in connection with the preparation of perfume and fragrance compositions.

The use of perfume ingredients in the manufacture of a wide variety of industrial products such as soaps, detergents, deodorants, cosmetic preparations and the like for purposes of imparting thereto an esthetically pleasing odor characteristic comprises, of course, well established practice. The commercial importance of perfume agents is, of course, to a great extent self evident and especially as regards applications primarily cosmetic in nature. However, in many instances, e.g., soaps and detergents manufacture, esthetic rather than functional considerations may well be determinative of product marketability and thus, considerations associated with product appearance, fragrance and the like assume rather critical importance.

Natural essential oils are widely exploited perfumery agents but have several disadvantages which detract from their commercial desirability. Hence, considerable industrial activity has centered around the research and development of synthetic perfume agents by suitable derivatization of natural occurring materials. Occasionally one comes across an abundant low cost essential oil with a major component which can be upgraded via suitable derivatives. One of the important advantages is the new body of matter is often a single controllable material free of the unavoidable variations connected with whole natural oils, differing from year to year and from lot to lot because they are obtained by variable primitive techniques. Moreover, a single chemical entity also affords a more predictable performance regarding compatability, stability, uniform fragrance strength and character in the multiplicity of end products in which perfumes are required. When such a derivative has great power coupled with low cost and a high degree of odor quality only obtainable by the use of expensive alternate materials, a valuable tool is presented to the perfumer.

Thus, a primary object of the present invention resides in the provision of a perfume and fragrance composition wherein certain disadvantages are eliminated and a novel perfume agent of superior functionality is provided.

Other objects and advantages of the present invention will become more apparent hereinafter as the description proceeds.

The attainment of the foregoing and related objects is made possible in accordance with the present invention which in its broader aspects includes the provision of a novel perfuming agent, compositions containing same as well as processing therefor and wherein said perfume agent comprises an ester which is the reaction product of longifolene and formic acid. 4

The longifolene-formic acid reaction product provided in accordance with the present invention possesses a pleasant, woody amber-like aroma. Of primary importance is the superior strength, character and low manufacturing cost compared to many other longifolene derivatives. Thus, the fragrance of the novel perfume agent described herein, in addition to being esthetically pleasing, provides an aroma of good intensity, the fragrance characteristics persisting for significant periods of time as evidenced by dry-out evaluation.

The longifolene-formic acid reaction product may be readily prepared by contacting at a temperature ranging from about 30C to about 90C, longifolene (C H i.e., 1,4-methanoazulene, decahydro-4,8,8- trimethyl-9-methylene, with formic acid in amounts sufficient to yield a mole ratio of formic acid to longifolene with the range of about 2 to about 10, said contacting being preferably carried out in the presence of an effective amount of a protonic acid such as sulfuric acid or a Lewis acid catalyst such as paratoluene sulfonic acid or methane sulfonic acid typified by boron trifluoride etherate, stannic chloride and the like and for a time sufficient to form the ester derivative; the latter may thereafter be recovered by any suitable separation technique, e.g., extraction, fractional distillation and the like.

The quantity of Lewis acid or protonic acid catalyst employed is not particularly critical apart from the requirement that it be present in effective amounts, i.e., quantities sufficient to permit the desired reaction rate. Thus, the catalyst component may be present in amounts varying from a small but effective amount, i.e., on the order of about 1 percent up to about 7 percent by weight of the formic acid.

The reaction may, if desired, be carried out in the presence of an inert solvent vehicle including, mobile liquid alkanes, e.g., propane, hexane, octane and the like; liquid aryl hydrocarbons, e.g., benzene, toluene, xylene, etc. However, since solvent materials are of an optional nature, their use is recommended against in order to minimize costs which would otherwise accrue in connection with necessary solvent-removal operations.

As previously indicated, the reaction is preferably carried out at a temperature within the range of from 30C to 90C. Within the aforestated range, specific values will be selected having reference to the reaction rate desired, the latter being influenced by the nature and type of solvent employed, if any, ratio reactants, amount of catalyst and the like. The temperature selected should not be so high as to result in undesirable side reactions or degradative decomposition of one or more of the involved ingredients or so low as to cause extended reaction times. In general, it is found that optimum results obtain with the use of temperatures within the range of 40C to 60C, and accordingly, such range is particularly preferred for use herein.

Product yield can be improved appreciably by employing a holding period with agitation following complete addition of the reactants and catalyst. The length of any such holding period will depend, for example, on reactant ratio, agitation level, etc. In general, holding periods substantially in excess'of l0 hours will not be required and particularly in view of the availability of modern, highly efficient processing equipment; thus, agitation is desirably carried out for periods ranging from about one hour to about 6 hours.

The formic acid reactant is preferably employed in molar excess in order to minimize quantities of unreacted longifolene, thereby facilitating product isolation and recovery while diminishing the formation of undesired byproducts. In accordance with preferred practice, the formic acid is employed in a molar excess of 2-10 or more times.

Pressure is not particularly critical in the practice of the present invention and thus, the reaction can be carried out under either subatmospheric or superatmospheric pressure conditions. However, such modes of proceeding require the use of specialized equipment which, in addition to the high cost involved, can prove burdensome from the standpoint of operation. Accordingly, it is in general preferred to employ atmospheric pressure.

The product can be recovered from the reaction medium by conventional means including washing, distillation, extraction, preparative chromatography, and the like. Fractional distillation under relatively high vacuum is particularly preferred, being especially conductive to effective separation and recovery. More specifically, upon completion of the desired reaction, it is generally recommended to wash the reaction mixture and to separate the organic layer. The aqueous layer can then be extracted with a suitable organic solvent such as benzene to recover the product as well as starting materials present therein. The organic solutions may then be combined and subjected to vacuum, fractional distillation whereby to provide the esterproduct.

The longifolene reactant employed in the aforedescribed process, comprises a cyclic terpene having the following structural formulaz H Longifolene is widely distributed in nature, notably among species of the genus Pinus. One of the sources of longifolene is so-called lndian terpentine oil obtained from Pinus longifolia Roxb. It occurs in such lndian terpentine oil in amounts of about 30 percent, and is preferably purified before use herein to purities on the order of 80 percent or more.

The novel fragrance material provided in accordance with the present invention can be employed to advantage in a wide variety of applications to impart a rich, precious wood fragrance.

As olfactory agents, such material can be formulated into or used as a component of a perfume composition. Thus, such material, in addition to having an esthetically pleasing fragrance, exhibits excellent stability in a wide variety of perfume articles and perfume compositions. The terminology perfume composition" as used in the context of the present invention, is intended to encompass a relatively wide variety of relationships. Thus, the composition in question may comprise an ultimate perfume product or alternatively, a fragranceimparting composition adapted to be incorporated into a finished perfume product for purposes of supplying a total fragrance impression or to enhance, modify or otherwise reinforce the natural fragrance characteristics of such product. Thus, suitable companion fragrance ingredients, i.e. auxiliary perfume adjuvants suitable for use in formulating the compositions contemplated herein include, for example, natural and synthetic oils, alcohols including both saturated and unsat urated alcohols, ketones, esters, lactones, aldehydes, ethers, anthranilatcs; acetals, terpenes; carboxylic acids, diphenyl compounds, hetcrocyclic compounds including azoles, quinolines, the macrocyclic musks including ketones. polycyclic musks including tetralin musks. Other ingredients which ma be suitablein a particular instance include, for example, solvents, dispersants, emulsifiers, surface-active agents, aerosol propellants and the like, depending upon the specific nature 0 bs Produc b in fq i t d v s det soap, space deodorant, cologne, bath preparation such as bath oil, bath salts; hair preparations such as lacquers, brilliantines, pomades and shampoos; cosmetic preparations such as creams, deodorants, hand lotions, sun screens; powders such as talcs, dusting powders, face powder and the like.

In preparing perfume compositions, the individual components contribute their particular olfactory characteristics, but the overall effect of the perfume composition will be the sum of the effect of each ingredient. Thus, the ester derivative of the present invention may be used to alter the aroma characteristics of a perfume composition, for example, by highlighting or moderating the olfactory reaction contributed by another ingredient of the composition. The term alter as used herein is intended to denote an effect on the fragrance impression, harmoniously blending with the other ingredient materials to produce a novel bouquet, or alternatively, enhancing, fortifying or reinforcing an existing fragrance note.

The amount of ester employed in a particular instance may vary over a relatively wide range and will be determined by a number of factors including, the nature and quantity of other ingredients, as well as the effects desired to be achieved. In any event, the essential requirement is that the ester reaction product be present in effective quantities, i.e., amounts sufficient to alter the fragrance of the composition, e.g., carrier or vehicle. Thus, it has been found that perfume compositions containing a small but-effective amount, e.g., as little as 2 percent by weight of the ester derivative, or even less, may be employed to advantage for purposes of imparting a pleasant wood aroma to soaps, cosmetics and other products. The amount employed can range up to 7% or higher, depending again upon the nature of the end product, the effect desired, as well as the particular fragrance sought. It will further be understood that the end product carrier or vehicle can be a liquid such as an alcohol, glycol or the like or alternatively, can be an absorbent solid such as talc or components for encapsulating the composition.

The following examples are given for purposes of illustration only and are not to be considered as necessarily constituting a limitation on the present invention.

EXAMPLE 1 PREPARATION OF LONGIFOLENE-FORMIC ACID REACTION PRODUCT To a 22 liter reaction flask fitted with stirrer, thermometer, addition funnel and reflux condenser with drying tube, are charged the following ingredients in the amounts specified.

Formic Acid Lon gifolene 4080 g. s g.

(88.7 moles) (40 moles) 2 liters of benlzene: The aqueous layer is decanted andextracted with 2 liters of benzene. The organic solutions are thereafter bulked and washed three times with 1.5 liters of a saturated aqueous solution of sodium bicarbonate. The benzene is then stripped off to a pot temperature of l C., atmospherically, yielding 8,748 g. of oil (acid value lA iil, ester value lS=4l.2 percent) containing about 35-40 percent of ester product. Fractional distillation of the crude oil in the presence of 3 percent Primol (refined mineral oil) and 0.1 percent lonox anti-oxidant at a pressure of 0.4 mm Hg, a reflux ratio of 2:1 and pot temperature of l00-l30C. through a 12 inch X 44 mm. Goodloe packed column serves to remove lower boiling fractions determined by gas-liquid chromatography (GLC) to constitute essentially isolongifolene, such determination being confirmed by nuclear magnetic resonance (NMR). The desired product is therefore obtained by fractionally distilling the residue through a 12 inch X 44 mm. Goodloe. packed column at a pressure of 0.3-0.7 mm. Hg at a reflux ratio of 9:1, (pot temperature l24l84C) and collecting the material having a boiling point of 8992C. Yield: 3,187.4 g.

The product has an ester value of 96.5 percent and LQQQBLSQHLPQ-fi jptq'viqsuqn estivs variation in the basic classic cologne blend, i.e., having a woody, amber-like fragrance note. Such fragrance exhibits good persistence on dry-out evaluation.

EXAMPLE 2 temperature is raised to 50C and the reaction mass' stirred at 50C for another 6 hours. The mixture is then poured into 1.5 liters of water and the organic layer separated. The aqueous layer is extracted with toluene, the combined organic layer is washed neutral and the solvent stripped off. Distillation of the residual oil yields 220 g. of isolongifolene and 120 g. of product. (Mainly a mixture of longifolene formates plus some alcohols'.)

Perfume compositions similar to that described as Example 1 but prepared with the longifolene formate a nil acid value. 25 of Example 2 have a pleasant, woody fragrance note A perfume of the following composition is prepared; and exhibit good persistance on dry-out evaluation.

' What is claimed is:

l. A perfume composition containing: (a) as an es- INGREDIENT AMOUNT (grams) sential ingredient, a fragrance altering amount of the product prepared by reacting longifolene and formic 28 acid at a temperature of from about 30C to 90C in the L jasmfim mm 3 presence of a protomc or Lewis acid catalyst, and (b) N lfigarde an auxiliary perfume adjuvant. Patchouli Oll 60 vanimn 6o 2. A perfume compositlon as defined lIl clalm l, Viol wherein said adjuvant is at least one material selected (The product of Example I) 60 l Lemon 0 80 from the group consisting-of natural perfume oils, syn- Rose Geranium Oil thetic perfume oils, alcohols, aldehydes, ketones, es- Lavender oil, French 120 Sweet orange oil 8 ters, lactones, ethers, anthranilates, acetals, carboxyllc M extract 50 j acids, aromatic hydroxy compounds, diphenyl com- Civet extract 3% 50 40 1000 pounds, azoles, qumolmes, terpenes, and musks. 

1. A PERFUME COMPOSITION CONTAINING: (A) AS AN ESSENTIAL INGREDIENT, A FRAGRANCE ALTERING AMOUNT OF THE PRODUCT PREPARED BY REACTING LONGIFOLENE AND FORMIC ACID AT A TEMPERATURE OF FROM ABOUT 30*C TO 90*C IN THE PRESENCE OF A PROTONIC OR LEWIS ACID CATALYST, AND (B) AN AUXILIARY PERFUME ADJUVANT.
 2. A perfume composition as defined in claim 1, wherein said adjuvant is at least one material selected from the group consisting of natural perfume oils, synthetic perfume oils, alcohols, aldehydes, ketones, esters, lactones, ethers, anthranilates, acetals, carboxylic acids, aromatic hydroxy compounds, diphenyl compounds, azoles, quinolines, terpenes, and musks. 